Microwave dielectric ceramic

ABSTRACT

A dielectric ceramic material consisting essentially of a composition of Formula 1
 
 x ATiO 3 (1 −x )Nd z Re (1−z) AlO 3    (1)
 
doped with 0.005% to 5% of a dopant selected from the group consisting of: cerium oxide, manganese oxide and mixtures thereof;
 
wherein A may be selected from the group consisting of: Ca, Sr, Mg and mixtures thereof;
 
Re may be selected from a group consisting of La, Sm, Pr, Dy, Er, Gd, Y and mixtures thereof;
 
wherein z is from 0.95 to 0.995; and
 
wherein x is a positive number less than 1.

This application claims priority under 35 U.S.C. §119 to the following United Kingdom patent applications: No. 0516421.5, filed Aug. 10, 2005; No. 0518736.4, filed Sep. 14, 2005; and No. 0519804.9, filed Sep. 29, 2005.

This invention relates to a dielectric ceramic material and also to a dielectric resonator comprising the novel ceramic material, the resonator being particularly useful for microwave application.

According to the present invention there is provided a dielectric ceramic material consisting essentially of a composition of Formula 1: xATiO₃+(1−x)Nd_(z)Re_((1−z))AlO₃  (1) doped with about 0.005 wt % to about 5 wt % of a dopant selected from the group consisting of: cerium oxide, manganese oxide and mixtures thereof; wherein A may be selected from the group consisting of: Ca, Sr, Mg and mixtures thereof; Re may be selected from a group consisting of La, Sm, Pr, Dy, Gd, Y, Er and mixtures thereof; wherein z is from 0.95 to 0.995; and wherein x is a positive number less than 1.

Materials in accordance with this invention find application in microwave base station filters (single and multimode). Preferred materials may be prepared which allow changes to relative permittivity ε_(r) and TCf values while retaining Q values>10,000 at about 2 GHz suitable for their intended applications.

Preferred materials in accordance with this invention possess high relative permittivity ε_(r) values in comparison to known materials with equivalent Q values. Particularly preferred materials have ε_(r) of 42-50, Q>10,000, for example>14,000, at about 2 GHz (e.g., 2.7 GHz) and TCf between −10 to +10 MK⁻¹.

Materials in accordance with this invention possess further advantages in relation to materials disclosed in the prior art, for example U.S. Pat. No. 5,356,844, because the ceramics of this invention have an improved microwave quality factor at ambient and higher operating temperatures.

Preferred materials consist essentially of a composition of Formula 2: xCa_(d)Sr_((1−d))TiO₃+(1−x)Nd_(z)Re_((1−z))AlO₃  (2)

-   -   doped with about 0.005% to about 5% of a dopant selected from         the group consisting of: cerium oxide, manganese oxide and         mixtures thereof;         -   wherein 0.5≦x≦0.9             -   0.25≦d≦1.0             -   0.95≦z≦0.995             -   1≦y≦2             -   Re may be selected from a group consisting of La, Sm,                 Pr, Dy and mixtures thereof and wherein             -   CeO₂ is added as a dopant in the range about 50 ppm to                 about 2.5 wt %.             -   MnO_(y) is added as a dopant in the range about 50 ppm                 to about 2.5 wt %.

Further preferred materials consist essentially of a composition of Formula 3: xCaTi_(1.03)O₃+(1−x)Nd_(0.95)Re_(0.05)AlO₃  (3)

-   -   wherein 0.65≦x≦0.72; y and Re are as stated above and wherein     -   CeO₂ is added as a dopant in the range about 50 ppm to about 2.0         wt %.     -   MnO_(y) is added as a dopant in the range about 50 ppm to about         1.0 wt %.     -   In preferred materials the ratio of Nd:Re is about 19:1.

An additional dopant selected from Fe₂O₃, Nb₂O₅, Ta₂O₅, Ga₂O₃ and mixtures thereof preferably Ga₂O₃ may be present in an amount of about 20 to about 5000 ppm, more preferably about 20 to about 2000 ppm.

The manganese oxide may be provided as the oxide or mixture of oxides or as a carbonate, oxalate or other thermally labile derivative.

The Ca, Nd, Al, Ti site occupancies may all be varied by +/−10%. In this specification MnO_(y) refers to the material after firing. Most Mn salts may be used to achieve the final MnO_(y).

The electrical properties for these ceramics can be summarised as follows: ε_(r)42−48

-   -   Q (2 GHz)>10,000     -   TCf (variable through composition)−10 to +10 MK⁻¹.

Compositions of the present invention may be manufactured by mixing the appropriate oxides, carbonates or oxalates or mixtures thereof in the above mentioned proportions, pulverising the mixture using a wet or dry method, calcining the mixture at a temperature of 1100° C. to 1400° C. for 1 to 16 hours, shaping the calcined mixture into an optional form and sintering the shaped body at a temperature of 1400° C. to 1700° C.

Percentages and other amounts referred to in this specification are by weight unless indicated otherwise.

The invention is further described by means of example but not in any limitative sense:

Experimental Procedure

All initial starting powders were of purity>99%. The raw materials were weighed in the appropriate quantities to form the compositions required. Deionised water or propan-2-ol was added to the weighed batches which were subsequently ball milled with magnesia stabilised zirconia milling media for 16 hours. Alternatively, the materials were attrition milled for 2 hours with yttria stabilised zirconia media. Subsequently, the raw material batches were dried at 80° C. and sieved through a 250 μm nylon mesh. The dried powder was calcined at temperatures in the interval 1100° C. to 1400° C. for 1 to 16 hours. The as-calcined powders were re-milled with 2 wt % PEG binder (MW 10000) for 8 hours, dried and sieved. Standard test samples of 9 g weight were uniaxially pressed in a 20 mm hardened stainless steel die using a pressure of˜150 MPa. Sintering of the pellets was performed between 1350 and 1600° C. for 1 to 48 hours under either an air or oxygen atmosphere. All samples were of density>95% theoretical density using the Archimedes water immersion technique.

The electrical properties were tested on the sintered components. Microwave dielectric properties were measured in reflection using the TE016 mode in a cubic silver plated cavity. TCf measurements were made in the interval +80° C. to −20° C. with the values of 60, 20 and −10° C. being used to calculate TCf. Er measurements were made using the parallel plate transmission technique of Hakki and Coleman.

EXAMPLE 1

Data mixtures of CaTiO₃ (CT) and Nd_(0.95)Sm_(0.05)AlO₃ (NSA); i.e a ratio of Nd to Sm of 19:1—aiming for a TCf between +6 and −6 MK⁻¹ were as shown in Table 1.

TABLE 1 Material Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.700 CT + 0.300 NSA 4.79 2.67 46.8 15300 40700 5.6 0.695 CT + 0.305 NSA 4.78 2.69 46.0 15300 41000 3.3 0.690 CT + 0.310 NSA 4.81 2.70 46.7 15300 41200 0.8 0.685 CT + 0.315 NSA 4.80 2.72 44.9 15300 41400 −1.5 0.680 CT + 0.320 NSA 4.83 2.74 45.3 15100 41400 −4.0

EXAMPLE 2

Variation in electrical properties as a function of Nd to auxiliary rare earth ratio: Properties of undoped CTNReA (0.700 CaTi_(1.03)O₃+0.300 Nd_(0.9)Re_(0.1)AlO₃) ceramics where the ratio of Nd to Re is equal to 9:1 are shown in Table 2.

TABLE 2 Density/ Material g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 100% Nd₂O₃ 4.77 2.67 46.6 15500 41400 6.0 Substitution of alternative rare earth for Nd in a ratio 10:1 CeO₂ 4.76 2.65 46.9 14700 39000 7.9 Sm₂O₃ 4.77 2.68 46.6 15600 41600 6.1 Pr₆O₁₁ 4.76 2.66 47.0 15500 41200 8.3 Dy₂O₃ 4.78 2.68 46.4 14000 37400 6.8 Y₂O₃ 4.71 2.68 46.2 14100 37700 5.3

EXAMPLE 3

Properties of undoped CTNReA (0.700 CaTi_(1.03)O₃+0.300 Nd_(0.95)Re_(0.05)AlO₃) ceramics where the ratio of Nd to Re is equal to 19:1 are shown in Table 3.

TABLE 3 Density/ Material g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 100% Nd₂O₃ 4.77 2.67 46.6 15500 41400 6.0 Substitution of alternative rare earth for Nd in a ratio 19:1 La₂O₃ 4.74 2.66 46.9 15300 40700 6.6 Sm₂O₃ 4.75 2.67 46.6 15300 40600 6.1 Pr₆O₁₁ 4.75 2.66 46.9 15300 40700 6.9

EXAMPLE 4

Properties of doped CTNReA (0.690 CaTi_(1.03)O₃+0.310 [Nd,Sm]AlO₃+0.5 wt % CeO₂) ceramics where the ratio of Nd to Sm is greater than 19:1 are shown in Table 4.

TABLE 4 Nd:Sm Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 99:1 4.80 2.70 45.3 15800 42600 −0.6 49:1 4.79 2.71 45.4 15800 42800 −0.6 32:1 4.80 2.70 45.4 15700 42400 −0.2 24:1 4.80 2.71 45.3 15900 43000 −1.0 19:1 4.80 2.73 45.4 15500 42100 −0.5

EXAMPLE 5

Properties of undoped CTNReA (0.700 CaTi_(1.03)O₃+0.300 Nd_(0.05)Re_(0.95)AlO₃) ceramics where the ratio of Nd to Re is equal to 1:19 are shown in Table 5.

TABLE 5 Density/ Material g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 100% Nd₂O₃ 4.77 2.67 46.6 15500 41400 6.0 Substitution of alternative rare earth for Nd in a ratio 1:19 La₂O₃ 4.65 2.57 49.9 14000 35850 22.0 Sm₂O₃ 4.81 2.69 45.7 15200 40900 7.9 Pr₆O₁₁ 4.68 2.60 48.8 14300 37200 24.9

EXAMPLE 6

Properties of undoped CTNPrA (0.660 CaTi_(1.03)O₃+0.340 [Nd,Pr]AlO₃) ceramics where the ratio of Nd to Pr is varied for zero TCf are shown in Table 6.

TABLE 6 Nd:Pr Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 1:19.0 4.84 2.76 44.0 14500 39800 1.1 1:18.0 4.80 2.73 44.8 14100 38500 6.6 1:17.0 4.76 2.70 45.7 13900 37400 13.0 1:16.0 4.72 2.66 46.8 13400 35700 20.0 1:15.5 4.70 2.65 47.5 12900 34200 25.5

EXAMPLE 7

Single doping of zero TCf material where Nd:Sm is 19:1.

Base material: 0.690 CaTi_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃

The data for MnO₂ doping are shown in Table 7(a)

TABLE 7(a) Density/ wt % MnO₂ g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.000 4.79 2.70 45.7 15300 41200 0.8 0.005 4.78 2.71 45.7 15300 41500 1.0 0.010 4.78 2.70 45.7 15400 41500 0.9 0.050 4.78 2.70 45.7 15000 40400 0.9 0.100 4.78 2.70 45.7 15000 40400 1.0 0.250 4.78 2.70 45.7 14200 38400 0.9

The data for CeO₂ doping are shown in Table 7(b)

TABLE 7(b) Density/ wt % CeO₂ g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.000 4.79 2.70 45.7 15300 41200 0.8 0.005 4.79 2.70 45.7 15600 42200 0.8 0.010 4.80 2.71 45.4 15600 42200 0.8 0.050 4.81 2.70 45.5 15700 42400 0.7 0.100 4.80 2.71 45.4 15600 42400 0.4 0.200 4.79 2.70 45.3 15700 42400 0.1 0.500 4.81 2.71 45.2 15700 42500 −0.7

The data for Co-doping with CeO₂ & MnO₂ are shown in Table 7(c)

TABLE 7(c) wt % CeO₂ & Density/ % MnO₂ g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.00 & 0.00 4.79 2.70 45.7 15300 41200 0.8 0.01 & 0.01 4.78 2.70 45.5 15300 41200 0.8 0.03 & 0.03 4.78 2.70 45.5 15200 41100 0.8 0.05 & 0.05 4.78 2.70 45.6 15200 40900 0.8 0.01 & 0.05 4.78 2.69 45.5 15300 41300 0.8 0.05 & 0.01 4.78 2.70 45.6 15100 40700 1.0

EXAMPLE 8

Single doping of zero TCf material where Nd:Sm or Nd:Pr is 1:19.

Base material: 0.690 CaTi_(1.03)O₃+0.310 Nc_(0.05)Sm_(0.95)AlO₃

TABLE 8(a) Density/ wt % CeO₂ g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.0 4.86 2.73 44.6 15400 42100 2.8 0.1 4.86 2.74 44.6 15300 41700 2.8 0.2 4.85 2.74 44.4 15400 42100 2.3 0.5 4.86 2.75 44.3 15500 42400 1.5

Base material: 0.660 CaTi_(1.03)O₃+0.340 Nd_(0.05)Pr_(0.95)AlO₃

TABLE 8(b) wt % CeO₂ Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.0 4.84 2.76 44.0 14500 39800 1.1 0.1 4.82 2.76 43.9 14400 39800 0.6 0.5 4.83 2.76 43.7 14500 40000 0.7

EXAMPLE 9

Additional doping trials:

(a) Fe₂O₃

Fe₂O₃ was added as an excess to the composition 0.690 CaTi_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃.

TABLE 9(a) wt % Fe₂O₃ Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.000 4.79 2.70 45.7 15300 41200 0.8 0.005 4.77 2.69 45.7 15500 41700 1.2 0.010 4.77 2.69 45.7 15500 41700 1.3 0.050 4.77 2.69 45.7 15300 41100 1.5 0.100 4.78 2.69 45.7 15100 40500 1.6 0.500 4.77 2.69 45.8 13400 36200 2.3 (b) SrO

SrO was added as a substitution for Ca in the composition 0.690 (Ca,Sr)Ti_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃+0.2 wt % excess CeO₂.

TABLE 9(b) mol % SrO Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz 0.0 4.79 2.70 45.7 15300 41200 1.0 4.77 2.69 45.9 14900 40200 2.0 4.79 2.69 45.9 15100 40500 5.0 4.82 2.70 46.1 14500 39200 10.0 4.86 2.68 46.7 14100 37800 20.0 4.93 2.67 47.6 12700 34000 (c) Nb₂O₅

Nb₂O₅ was added an excess to the composition 0.690 CaTi_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃

+0.2 wt % excess CeO₂.

TABLE 9(c) wt % Nb₂O₅ Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.0 4.79 2.70 45.7 15300 41200 0.8 0.1 4.77 2.70 45.7 15600 42100 1.2 0.2 4.77 2.70 45.7 15600 42000 1.3 0.5 4.77 2.70 45.9 15300 41200 1.5 (d) Ta₂O₅

Ta₂O₅ was added an excess to the composition 0.690 CaTi_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃

+0.2 wt % excess CeO₂.

TABLE 9(d) wt % Ta₂O₅ Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.0 4.79 2.70 45.7 15300 41200 0.8 0.1 4.78 2.71 45.6 15600 42300 1.0 0.2 4.78 2.69 45.7 15600 41900 1.2 0.5 4.78 2.70 45.7 15700 42500 1.1 (e) Ga₂O₃

Ga₂O₃ was added as both an excess and a substitute for Ti in the composition 0.690 CaTi_(1.03)O₃+0.310 Nc_(0.95)Sm_(0.05)AlO₃+0.2 wt % excess CeO₂.

TABLE 9(e) Density/ TCf/ % Ga₂O₃ g cm⁻³ f/GHz ε_(r) Q Qf/GHz MK⁻¹ 0.000 4.79 2.70 45.7 15300 41200 0.8 0.005 on Ti site 4.77 2.70 45.4 16100 43500 −0.1 0.010 on Ti site 4.77 2.70 45.1 16200 43800 −0.8 0.100 wt % excess 4.77 2.70 45.6 15900 42700 1.0 0.200 wt % excess 4.77 2.69 45.7 15900 42700 1.1 0.500 wt % excess 4.77 2.69 45.6 15700 42200 1.5

EXAMPLE 10

Influence of cation stoichiometry upon electrical properties:

(a) Ca

The composition range examined was 0.690 Ca_(z)Ti_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃+0.2 wt % excess CeO₂, where z varied between 0.95 and 1.05.

TABLE 10(a) z Ca Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.95 4.78 2.67 46.8 14000 37400 6.8 0.97 4.78 2.68 46.4 14500 38800 4.4 0.99 4.78 2.69 46.0 15100 40700 1.9 1.00 4.79 2.70 45.7 15300 41200 0.8 1.01 4.77 2.71 45.2 15600 42100 −0.7 1.03 4.61 2.76 42.5 12600 34700 −2.0 1.05 4.74 2.74 44.2 14700 40300 −4.7 (b) Ti

The composition range examined was 0.690 CaTi_(z)O₃+0.310 Nd_(0.95)Sm_(0.05)AlO₃+0.2 wt %

excess CeO₂, where z varied between 0.98 and 1.08.

TABLE 10(b) z Ti Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.98 4.76 2.78 43.0 14400 40000 −9.7 1.00 4.69 2.78 42.9 12400 34300 −5.3 1.02 4.78 2.72 45.1 15500 42200 −1.5 1.03 4.79 2.70 45.7 15300 41200 0.8 1.04 4.78 2.70 46.2 15100 40600 2.9 1.06 4.78 2.66 47.0 14500 38400 7.6 1.08 4.79 2.64 48.0 13900 36500 12.2 (c) Al

The composition examined was 0.690 CaTi_(1.03)O₃+0.310 Nd_(0.95)Sm_(0.05)Al_(z)O₃+0.2 wt % excess CeO₂, where z varied between 0.95 and 1.05.

TABLE 10(c) z Al Density/g cm⁻³ f/GHz ε_(r) Q Qf/GHz TCf/MK⁻¹ 0.95 4.46 NR — — — — 0.97 4.78 2.70 45.7 15400 41500 0.4 0.99 4.78 2.70 45.6 15600 41900 0.4 1.00 4.79 2.70 45.7 15300 41200 0.8 1.01 4.78 2.70 45.6 15400 41600 0.7 1.03 4.78 2.70 45.6 15400 41400 1.1 1.05 4.78 2.71 45.5 15100 40800 1.4 NR—no resonance detected

EXAMPLE 11

1 and 2 GHz parts:

Commercial size resonators were developed from the following composition: 0.69CaTi_(1.03)O₃+0.31Nd_(0.95)Sm_(0.05)AlO₃+0.2 wt % excess CeO₂.   Comp A

The electrical response of ceramics prepared from the above composition A were evaluated against an undoped material of composition: 0.69CaTi_(1.03)O₃+0.31NdAlO₃  Comp B

The measured Q-values were as follows:

TABLE 11 Freq/GHz Comp A Comp B % Differential 1.0 34600 33000 4.6 2.0 21000 20300 3.3 2.7 16000 15600 2.5

EXAMPLE 12

Dopant and influence on Q-value at elevated temperatures:

-   -   Composition: Comparison of Q-value at ambient and elevated         temperature for compositions A and B (0.69 CaTi_(1.03)O₃+0.31         Nd_(0.95)Sm_(0.05)AlO₃)

TABLE 12 Temperature/″ C. Q-value of Comp A Q-value of Comp B 22 16000 15600 80 13900 13500 120 12800 12400 150 12000 11600

Although the foregoing invention has been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the compositions of the present invention. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein, but may be modified within the scope and equivalents of the appended claims.

The entire disclosures of all references cited herein are incorporated by reference for all purposes. 

1. A dielectric ceramic material consisting essentially of a composition of formula 1: xATiO₃+(1−x)Nd_(z)Re_((1−z))AlO₃  (1) doped with about 0.005% to about 5% of a dopant selected from the group consisting of: CeO₂, MnO_(y) and mixtures thereof; wherein A is selected from the group consisting of: Ca, Sr, Mg and mixtures thereof; Re is selected from a group consisting of La, Sm, Pr, Dy, Gd, Y, Er and mixtures thereof; wherein z is from 0.95 to 0.995; wherein x is a positive number less than 1 and 1≦y≦2.
 2. A dielectric ceramic material as claimed in claim 1 with a composition of formula 2: xCa_(d)Sr_((1−d))TiO₃+(1−x)Nd_(z)Re⁽¹⁻ z)AlO₃  (2) doped with about 0.005% to about 5% of a dopant selected from the group consisting of: CeO₂, MnO_(y) and mixtures thereof; wherein 0.5≦x≦0.9 0.25≦d≦1.0 0.95≦z≦0.995 1≦y≦2 Re is selected from a group consisting of La, Sm, Pr, Dy, Gd, Y, Er and mixtures hereof and wherein CeO₂ is added as a dopant in the range about 50 ppm to about 2.5 wt %. MnO_(y) is added as a dopant in the range about 50 ppm to about 2.5 wt %.
 3. A dielectric ceramic material as claimed in claim 1 with a composition of formula 3: xCaTi_(1.03)O₃+(1−x)Nd_(0.95)Re_(0.05)AlO₃  (3) wherein 0.60≦x≦0.72 and y are as stated above and Re is Sm or Pr and wherein CeO₂ is added as a dopant in the range about 50 ppm to about 2.5 wt %, and MnO_(y) is added as a dopant in the range about 50 ppm to about 2.5 wt %.
 4. A dielectric ceramic material as claimed in claim 3, wherein 0.65≦x≦0.72, Re is Sm and CeO₂ is added as an excess dopant in an amount of 0.2 wt %.
 5. A dielectric ceramic material as claimed in claim 1 with a composition of formula 4: xCaTi_(1.03)O₃+(1−x)Nd_(0.05)Re_(0.95)AlO₃  (4) wherein 0.60≦x≦0.72 and y are as stated above and Re is Sm or Pr and wherein CeO₂ is added as a dopant in the range about 50 ppm to about 2.5 wt %, and MnO_(y) is added as a dopant in the range about 50 ppm to about 2.5 wt %.
 6. A dielectric ceramic material as claimed in claim 5, wherein 0.60≦x≦0.72, Re is Sm and CeO₂ is added as an excess dopant in an amount of from 0.01 wt % to 1.0 wt %.
 7. A dielectric ceramic material as claimed in claim 5, wherein 0.60≦x≦0.72: Re is Pr and CeO₂ is added as an excess dopant in an amount of from 0.01 wt % to 1.0 wt %.
 8. A dielectric ceramic material as claimed in claim 3 wherein Sr, Mg or a mixture thereof are substituted for Ca in an amount of 0 to 20 mol % and wherein 0.85≦x≦1.0.
 9. A dielectric ceramic material as claimed in claim 1, further comprising an additional dopant in an amount of 20 to 5000 ppm, wherein the additional dopant is selected from the group consisting of: Fe₂O₃, Nb₂O₅, Ta₂O₅, Ga₂O₃ and mixtures thereof.
 10. A dielectric ceramic material as claimed in any preceding claim 2, including further comprising an additional dopant in an amount of 20 to 5000 ppm, wherein the additional dopant is selected from the group consisting of: Fe₂O₃, Nb₂O₅, Ta₂O₅, Ga₂O₃ and mixture thereof.
 11. A dielectric ceramic material as claimed in any preceding claim 3, including further comprising an additional dopant in an amount of 20 to 5000 ppm, wherein the additional dopant is selected from the group consisting of: Fe₂O₃, Nb₂O₅, Ta₂O₅, Ga₂O₃ and mixture thereof.
 12. A dielectric ceramic material as claimed in claim 9, wherein the additional dopant is Ga₂O₃.
 13. A dielectric ceramic material as claimed in claim 12, wherein the amount of Ga₂O₃ is from 20 to 2000 ppm.
 14. A dielectric ceramic material as claimed in claim 3, wherein the cation site occupancy of Ca, Ti, Nd and Al is varied by ±10%.
 15. A dielectric ceramic material as claimed in claim 1, wherein the material has electrical properties summarised as follows: ε_(r)42−48 Q (2 GHz)>10,000 TCf (variable through composition)−10 to +10 MK⁻¹.
 16. A dielectric ceramic material as claimed in claim 1, wherein the material has electrical properties summarised as follows: ε_(r)42−48 Q (2.7 GHz)>14,000 TCf (variable through composition)−10 to +10 MK⁻¹.
 17. A dielectric resonator comprising a dielectric ceramic material as claimed in claim
 1. 18. A dielectric resonator as claimed in claim 17 with a composition of formula
 2. 19. A dielectric resonator as claimed in claim 17 with a composition of formula
 3. 20. A dialectic resonator as claimed in claim 17, wherein the dielectric ceramic material has electrical properties summarised as follows: ε_(r)42−48 Q (2 GHz)>10,000 TCf (variable through composition)−10 to +10 MK⁻¹. 